pilot testing of a modular system for oxygen production...project objectives objectives: the design,...

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Pilot Testing of a Modular System for Oxygen

Production

DOE Cooperative Agreement DE-FE-0031527

NETL Gasification Virtual Peer Review

September 2, 2020

Project objectives

Objectives: The design, fabrication, and testing of a 10 to 20 kg/day modular oxygen (O2) production

system

▪ Be cost competitive with current state-of-art process

▪ Modular process for small scale oxygen production

▪ Sorbent bed-factor less than 600 lb-sorbent/TPD O2 (tons/day O2)

▪ O2 purity greater than 95%

Specific Challenges

▪ Rapid PSA cycle development

▪ Structured sorbent module development

▪ Rapid cycle modeling tool development and cycle optimization

▪ Material and module scale up and manufacturing

▪ Design and fabrication of pilot O2 production system

▪ Parametric and long-term testing

▪ Techno-economic analysis

2

Material

Synthesis

Material

Design

Material

Forming

Advanced

Structures

Cycle

Development

Commercial

Materials

Integrated

Testing

Commercial

Applications

Success criteria

3

Success Criteria

Determination of optimized O2 sorbent formulation and engineered bed (module) structure for this sorbent to

scale up to pilot production, as supported by Task 2 experimental results and Task 3.1 rapid-cycle process

model projections

1. Structured sorbent mechanically robust and stable after >1,000 rapid sorption/desorption cycles

2. Either the O2 binding sorbent or the conventional sorbent has sufficient working capacity for an O2

production system with predicted BSF<600.

Process design package & final techno-economic analysis for full-scale, modular, rapid-cycle PSA O2

production system using novel structured sorbent to produce 10-50 TPD of high-purity (≥95%) O2 from air as

the oxygen feed for DOE’s 1- to 5-MW oxygen-blown REMS gasifier skid for power generation

1. Target O2 production cost below SOTA (target is < $45/ton)

Target Bed Size Factor [BSF] ~ 600

(smaller than benchmark BSF of 850 for commercial VPSA for O2 production)

Development Roadmap

4

Project team

5

6

Materials Scale-up

Bio-Inspired O2 Sorbent Material Development Summary

7

TGA Cyclic O2 Sorption of RTI’s RTI-O2Sorb1 vs. Commercial Co-Salen

8

RTI-O2Sorb1_Activated at 100 °C




Progress on Scale-up of RTI-O2Sorb

9

✓ Successfully repeated batch synthesis for maximum O2 sorption performance

(reversible O2 uptake of 1~1.5 wt% with powder sample after activation at 170 oC)

✓ Successfully synthesized powder material with same performance using Schlenk line

(which allows large batch synthesis)

✓ Successfully scaled up powder material synthesis with same sorption performance

(20g → 40 g → 120 g → 240 g per batch)

ExtrusionGranulation Pelletization

10

Agglomeration of Powder into Structured Form

Optimization of Extrudate Formulation

Extrudate Formation Characteristics

12

0

2

4

6

8

10

12

14

Cru

sh

str

en

gth

(N

/mm

)

Recipe

BA C D E

Key characteristics of Forming Extrudate:• O2 capacity, mechanical strength, size

Key variables of Forming Extrudate:• binder ratios and solvent

• extrusion pressure and temperature, drying

temperature

Binder (wt%) Density (g/cc) Dia. (mm)

Length (mm)

Crush strength (N/mm)

Dynamic oxygen capacity (wt%)

16.7 0.55-0.62 1.2-1.5 2.0-10.0 8.0-12.0 0.8-1.2

0

50

100

150

200

Tem

pera

ture

(°C

)

60

62

64

66

68

Weig

ht (m

g)

0 500 1000 1500 2000

Time (min)

Sample: 14186-172Size: 66.1110 mgMethod: jpmethod 030 Ar-O2Comment: 1.1 mm extrudate

TGAFile: C:...\JP tests 724\14186-172.001

Run Date: 11-Mar-2020 15:00Instrument: TGA Q500 V20.13 Build 39

Universal V4.5A TA Instruments

1.10wt% @ Cycle 10

TGA Profile of Extrusion Shaped RTI-O2Sorb (crushed to 300~425 µm)

13

23.89mg

23.68mg

0

50

100

150

200

Te

mp

era

ture

(°C

)

22

24

26

28

We

igh

t (m

g)

0 100 200 300 400 500 600

Time (min)

Sample: 14186-123BSize: 27.7990 mgMethod: jpmethod 030 Ar-O2Comment: extrudate and crushed sived 14186-123B N2 dried

TGAFile: C:...\JP tests 724\14186-123B.001

Run Date: 18-Sep-2019 17:37Instrument: TGA Q500 V20.13 Build 39

Universal V4.5A TA Instruments

10 min cycle

0.89wt%

10 min cycle

1.25wt%

Exposure/Aging Testing

• 2.62 vol% H2O (g), balance N2

• 45d exposed, similar to long term cycling

• 1.5% O2,19.5 CO2, balance N2

• Exposed 36d – no degradation

• 2.62 vol% H2O (g), 20.40% O2, balance N2

• Similar to long term cycling in TGA

• 99% vol% O2, , balance N2

• Some degradation through day 12,

• day 30 similar to day 12 ( See graphic to left)

Figure 5. O2 and N2 sorption/desorption isothermal curves with different aging time: (a) fresh; (b) 12

15

Forming of Structured Sorbents

Air Liquide Objectives:

• Develop novel structured adsorbents production techniques using conventional sorbent materials

• Apply and adapt the techniques developed on conventional adsorbents to the novel oxygen-binding

adsorbent materials

• Manufacture and ship 2 to 4 structured adsorbers for pilot testing based on novel oxygen-binding adsorbent

• Support activities (e.g. Pilot design, Techno-Economic Analysis)

Sorbent and Structured Sorbent Module Development and Characterization

16

Highlights of BP1

• Air Liquide BP1 objectives successfully met on time (by June 30th, 2019)

• Formulations were developed and characterized for (1) air dehumidification and (2) for

conventional nitrogen (N2)-binding adsorbent

• Activation protocols for each adsorbent formulation were developed

• Forming techniques to produce structured beds were developed

Highlights of BP2 so far

• Forming techniques and activation tool were scaled up for beds of up to 1 kilogram

• Reviewed and provided feedback on the pilot design

• Ongoing work on adapting formulation and forming techniques to novel oxygen-binding

adsorbent. Multiple samples were received from RTI, characterized and used to support

adaptation-work on formulation and forming

BP1 – Overall Approach

• Conventional O2 VSA ➔ uses 2 adsorbents

• Top adsorbent used to capture N2

• Bottom adsorbent used for air drying

• Structured beds made of elementary shapes

• Elementary shapes produced by combining adsorbent

powder and binder


17

BP1 – Air Drying / Multi-Steps Approach

• 2 options: activated alumina (AA) or silica gel (SG)

• SG powder selected based on its highest water capacity

• SG powder formed with a binder into elementary shapes

BP1 – Air Drying / Multi-Steps Approach

• H2O capacity of SG elementary shapes meets expectations

• Small scale structured SG-bed formed and characterized

– H2O breakthough curve comparable to conventional beaded bed

– Pressure drop comparable to conventional beaded bed


18

BP1 – N2 Adsorbent / Multi-Steps Approach

• Various zeolites typically used as N2 binding

adsorbents

• Selection of zeolite powder

• Forming with binder

• High temperature activation

• Similar N2 capacity & selectivity compared to

commercial adsorbents

• Faster kinetics


19

BP2 – Ongoing Adaptation Work on Novel O2 Binding Adsorbent

• Goal: form structured bed with novel adsorbent by adapting techniques developed

over BP1

• First powdery samples of novel adsorbent received from RTI early Q2 2020

• Current focus is on producing an advantageous elementary shape while managing

specific limitations of novel adsorbent

• An advantageous elementary shape is fast to produce and can yield low pressure

drop once formed into a structured bed

• Performance of the formed adsorbent is checked by running N2/O2 isotherms on

elementary shapes

• Next Steps

– Finalize definition of elementary shapes based on lab trials

– Performance check of elementary shapes based on N2/O2 isotherms

– If formed-adsorbent performance meets expectations, then structured beds will be formed

and shipped for pilot testing


20

Novel powder of O2 binding adsorbent

21

Cycle Modeling

Development of a vacuum pressure-swing adsorption (VPSA) full-order solver

22

Optimization

Process modeling

• Competitive adsorption equilibria modeled w/ IAST

• Linear driving-force (LDF) approximation for mass transfer

• 1D PDE system describing transient fixed-bed

adsorber equations for 7 state variables: gas-phase

compositions, adsorbed-phase concentrations,

pressure, bed & casing temperatures

• Coded in MATLAB

• Solved numerically w/ Finite Volume Method (FVM)

Adsorption equilibria

• Multi-objective optimization of relevant VPSA performance

variables using genetic & surrogate-based algorithms

• Applied a short-cut

method to test IAST

implementation and

obtain preliminary

assessment for the

oxygen-binding

adsorbent

• First-principles heat transfer modeling considered

Process modeling results

23

• Dynamic column breakthrough (DCB)

Flue-gas separation results for model validation

• 4-step VPSA w/ LPP for heavy-product recovery

On-going sub-tasks

• Implementation of 6-step cycle to simulate the operation

of the air separation skid under construction

• Efficiency improvements of IAST calculations to speed-up

optimization runs

• Implementation & execution of multi-objective

optimization runs for 4-step and 6-step cycles to identify

suitable operating conditions

24

Integrated Test Skid

10 kg Pilot Modular System Process Flow Diagram

25

• O2 production rate

• O2 purity

• Cycle optimization

• Bed size factor

• Unit power consumption

• Material stability

• Techno-economic analysis

for O2 cost projectionHouse Air

Vent

RTI INTERNATIONAL

TAC DIVISION

Drawing Name

RTI O2 Testing System

Pressure Swing Adsorber

1000216240.000.005Project Number Drawing Number

Drawn By Date

P. Mobley 11/27/2019Rev.

3

Revision History# Date By App

Set @150 psig

360

PCV

360

FI

110

FCV

110

FIC

320

PT

320

PI

310

V

110

F

110

HV

110

CV

360

AE

360

AIT

360

AI

O2

360

PT

360

PIC

200

PSV

360

CV

320

PI

ATo Vent

310

PT

310

PI

310

PI

250

VP

325

TE

325

TIC

321

TE

321

TI

322

TE

322

TI

323

TE

323

TI

324

TE

324

TI

200

PT

200

PI

110

SV

110

D

201

SV

280

SV

210

SV

220

SV Vent

260

PCV

260

FI

260

AE

260

AIT

260

AI

O2

260

PT

260

PIC

260

CV

260

V

212

SV

222

SV

House N2

120

FCV

120

FIC

120

F

120

HV

120

CV

120

SV

Cyl. O2

130

PCV130A

PI

130

FCV

130

FIC

130

F

130

HV

130

CV

130

SV

211

SV

221

SV

A

B

290

SV

B

135

SV

125

SV

135

CV

125

CV

130B

PI

Purge Gas

150

FCV

150

FIC

Cyl. He

140

PCV140A

PI

140

FCV

140

FIC

140

F

140

HV

140

CV

140

SV140B

PI

311

SV

321

SV

To Vent

Notes:1. Valves and vent line to be routed down and have drain valve at low point2. Valves to be located as close as possible to V-310, V-320, V-330, V-340

325

HE

325

TY

325

TSSH

325S

TE

315

TE

315

TIC

311

TE

311

TI

312

TE

312

TI

313

TE

313

TI

314

TE

314

TI

315

HE

315

TY

315

TSSH

315S

TE

310

SV

320

SV

312

SV

322

SV

355

SV

Note 1

3

1

24

220

PT

220

PI

210

PT

210

PI

220

PI

210

PI

250

C

260

SV

360

V

3

1

24

360

SV

251

SV

3

1

24

300

SV

361

PT

361

PI

261

PT

261

PI

N2

O2

255

SV

345

TE

345

TIC

341

TE

341

TI

342

TE

342

TI

343

TE

343

TI

344

TE

344

TI

231

SV

241

SV

331

SV

341

SV

345

HE

345

TY

345

TSSH

345S

TE

335

TE

335

TIC

331

TE

331

TI

332

TE

332

TI

333

TE

333

TI

334

TE

334

TI

335

HE

335

TY

335

TSSH

335S

TE

330

SV

340

SV

320

V

330

V

340

V

340

PT

340

PI

340

PI

330

PT

330

PI

330

PI

332

SV

342

SV

230

SV

240

SV

232

SV

242

SV

240

PT

240

PI

230

PT

230

PI

240

PI

230

PI

351

SV

3

1

24

250

SV

253

SV

252

SV

Set @150 psig

260

PSV

Set @150 psig

360

PSV

Steps

• HMB - completed

• Sizing – completed

• Safety Review Internal – completed

• AL feedback – completed

• Order Key Instruments - completed

• Fabrication\Controls - Ongoing

• Commissioning

• Testing

TEA Refinement

▪ Data from the 10 kg/d test bed will provide key data for sorption/desorption kinetics at relevant

conditions

– O2-binding sorbent data will be used for cycle modeling and optimization by GTRC

– N2-binding, if tested, will be modeled by Air Liquide

▪ Air Liquide will provide input module costs

▪ System design will be updated from DE-FE0027995 (10 TPD design) to incorporate

– Refined sizing and utilities

– Update utilities and equipment cost

– Update modular construction costs

– Determine overall O2 production cost

26

For DOE Internal Use Only

Outcomes

Results

▪ Converted RTIO2Sorb synthesis from glove box to scalable protocol

▪ Developed structured sorbent modules with N2 sorbents

▪ Developed O2 sorbent VPSA cycle model

▪ Design of 10 kg/d testing system

Next step

▪ Integrated 10 kg/d system testing

▪ Incorporate RTIO2Sorb into structured sorbent modules

▪ Refining process modeling for large scale design and cost

Future

▪ Catalyst manufacturing development

▪ Large pilot-scale testing or 1 TPD prototype

27

Enable small-scale

applications of oxygen such

as 10-30MW gasifiers or 1 to

10 TPD systems by providing

air separation at small-scale

matching air separation cost

of larger cryogenic

separation systems.

Acknowledgements

28

RTI International

Dr. John Carpenter

Dr. Jianping Shen

Dr. Qinghe (Angela) Zheng

Dr. Jak Tanthana

Dr. Paul Mobley

Dr. Jian Zheng

Dr. Vijay Gupta

Dr. Mustapha Soukri

Jonathan Peters

GTRC

Dr. Matther Realff

Dr. Hector Octavio Rubiera Landa

Contact Information:

Dr. John Carpenter

919.541.6784

[email protected]

DOE/NETL Cooperative Agreements

DE-FE0031527

DOE\NETL

Diane Madden

Air Liquide

Raja Swaidan

Philippe Coignet

pilot testing of a modular system for oxygen production...project objectives objectives: the design,...

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